Photographic light-sensitive material

ABSTRACT

A silver halide photographic light-sensitive material is described containing a compound comprising at least one unsaturated group and at least one betaine group in at least one layer thereof. The photographic light-sensitive material has a high sensitivity without being accompanied by an undesirable increase in the formation of fog.

BACKGROUND OF THE INVENTION

The present invention relates to a photographic light-sensitive materialand more particularly to a chemically sensitized silver halidephotographic light-sensitive material.

Various means of chemical sensitization for increasing the lightsensitivity of silver halide photographic emulsions are known. Onetypical method is known as sulfur sensitization, wherein the lightsensitivity of a silver halide photographic emulsion is increased byadding thereto a very small amount of sulfur or a sulfur compound toform silver sulfide, as disclosed, for example, in U.S. Pat. Nos.2,410,689 and 3,501,313, West German Pat. No. 1,422,869, and JapanesePat. No. 20533/74.

Also, methods for increasing the light sensitivity of silver halidephotographic emulsions by adding thereto a suitable reducing agent orgold compound, known as reduction sensitization and gold sensitization,respectively, are disclosed, for example, in U.S. Pat. Nos. 2,399,083and 3,297,446.

Furthermore, it is known to increase the light sensitivity of silverhalide emulsions by a combination of these sensitization methods, asdescribed in T. H. James, The Theory of the Photographic Process, 4thEdition, pp. 149-160 (Macmillan Pub. Co., 1977).

In these conventional sensitization methods, as the amount of sensitizeris increased to obtain higher light sensitivity, the silver halidephotographic emulsions tend to form fog, and it becomes difficult tocontrol the formation of fog even by using antifoggants or stabilizers.Also, silver halide photographic emulsions sensitized by suchconventional sensitization methods suffer from the disadvantage thatwhen photographic films prepared by coating such silver halide emulsionsare stored under high temperature and high humidity conditions, thephotographic characteristics change greatly.

Attempts to improve the light sensitivity of silver halide emulsions byprolonging the chemical ripening period or increasing the ripeningtemperature are accompanied by an increase in the formation of fog, andit has been difficult to attain the desired purpose.

It is known to use a surface active agent having a betaine group as acoating aid for a photographic light-sensitive material, as described inU.S. Pat. No. 3,843,368. But such surface active agent does not haveability to increase the light sensitivity of silver halide emulsions.

SUMMARY OF THE INVENTION

It is, accordingly, a first object of the present invention to provide aphotographic light-sensitive material, the sensitivity of which has beenimproved without being accompanied by an increase of fog harmful to thephotographic characteristics.

A second object of the present invention is to provide a photographiclight-sensitive material which is less subject to a reduction insensitivity when stored under high temperature and high humidityconditions.

A third object of the present invention is to provide a method forincreasing the sensitivity of a photographic light-sensitive materialwithout an increase in fog harmful to the photographic characteristics.

These and other objects of the present invention, that will become moreapparent from the following detailed description and Examples, areachieved by a silver halide photographic light-sensitive materialcomprising a support having coated thereon at least one silver halideemulsion layer, said photographic light-sensitive material containing acompound comprising at least one unsaturated group and at least onebetaine group and having substantially no surface activity in at leastone layer thereof.

DETAILED DESCRIPTION OF THE INVENTION

The above and other objects of the present invention can be attained byincorporating a compound, which is represented by the formula (I)hereinbelow and which has substantially no surface activity, into atleast one of the constituent layers of the photographic light-sensitivematerial. ##STR1## wherein R₁, R₂, and R₃, which may be the same ordifferent, each represents hydrogen, an alkyl group (preferably havingfrom 1 to 6 carbon atoms, and most preferably having from 1 to 4 carbonatoms), a carboxy group or a substituted alkyl group (preferably havingfrom 1 to 6 carbon atoms, and most preferably having from 1 to 4 carbonatoms, with the substituent being a hydroxy group, a halogen atom, anitro group, etc.); R₄ and R₅, which may be the same or different, eachrepresents hydrogen, an alkyl group (preferably having from 1 to 6carbon atoms, and most preferably having from 1 to 4 carbon atoms), asubstituted alkyl group (preferably having from 1 to 6 carbon atoms, andmost preferably having from 1 to 4 carbon atoms, with the substituentbeing a hydroxy group, a halogen atom, a nitro group, etc.) or anaralkyl group (preferably having from 7 to 11 carbon atoms), or R₄ andR₅ together represent an atomic group necessary to form a heterocyclicring (for example, a morpholine ring, etc.), or R₄ or R₅ is bonding withA and represent an atomic group necessary to form a heterocyclic ring(for example, a pyridine ring, an imidazole ring, etc.) (theheterocyclic ring may be substituted, with the substituent preferablybeing an alkyl group, a hydroxy group, a halogen atom, a nitro group,etc.); R₆, R₇, R₈, and R₉, which may be the same or different, eachrepresents hydrogen, an alkyl group (preferably having from 1 to 6carbon atoms, and most preferably having from 1 to 4 carbon atoms) or asubstituted alkyl group (the substituent being a hydroxy group, ahalogen atom, a nitro group, etc.); A represents a divalent connectinggroup, and particularly preferably an ether group, an alkylene group(preferably having from 1 to 6 carbon atoms), a substituted alkylenegroup (preferably having from 1 to 6 carbon atoms, and the substituentbeing a hydroxy group, a halogen atom, a nitro group, etc.), an arylenegroup (preferably having from 6 to 11 carbon atoms), a substitutedarylene group (preferably having from 6 to 11 carbon atoms, and thesubstituent being a hydroxy group, a halogen atom, a nitro group, etc.),an aralkylene group (preferably having from 8 to 12 carbon atoms), asubstituted aralkylene group (preferably having from 8 to 12 carbonatoms, and the substituent being a hydroxy group, a halogen atom, anitro group, etc.), a --COOR₁₀ -group (wherein R₁₀ represents a divalentgroup, preferably an alkylene group, and particularly preferably analkylene group having from 1 to 6 carbon atoms; an arylene group, andparticularly preferably an arylene group having from 6 to 11 carbonatoms; an aralkylene group, and particularly preferably an aralkylenegroup having from 8 to 12 carbon atoms; or an atomic group forming aheterocyclic ring together with R₄ or R₅), a --OCO--R₁₀ -group, a##STR2## (wherein R₁₁ represents hydrogen; an alkyl group, preferably analkyl group having from 1 to 6 carbon atoms; or an atomic group formingin heterocyclic ring together with R₄ and R₁₀, or R₅ and R₁₀ ; or anatomic group forming a heterocyclic ring (for example, a pyridine ring,an imidazole ring, etc.) together with R₄ or R₅); a and b eachrepresents 0 or a positive integer (preferably from 1 to 6, andparticularly preferably from 1 to 4) provided that a and b are not both0; and B represents --COO or --SO₃.

The compound of the formula (I) used in the present invention hassubstantially no surface activity. The "substantially no surfaceactivity" means in the present invention that surface tension of 1 wt%aqueous solution of the compound is 45 dyne/cm or more.

Particularly preferred compounds are those represented by formula (I)wherein R₁, R₂, and R₃ each represents hydrogen, a lower alkyl group, ora carboxy group; R₄ and R₅ each represents a lower alkyl group, anatomic group forming a pyridine ring or an imidazole ring together withA, or R₄ and R₅ together represent an atomic group forming a morpholinering; R₆, R₇, R₈, and R₉ each represents hydrogen or a methyl group; Arepresents ##STR3## or an atomic group forming a pyridine ring or animidazole ring together with R₄ or R₅ ; and a and b each represents 0 ora positive integer from 1 to 4.

Of the betaine compounds represented by formula (I), representativeexamples of these compounds which are preferably used in the presentinvention are illustrated below, but the present invention is not to beconstrued as being limited thereto. ##STR4##

The compounds which can be used in the present invention can besynthesized with reference to the methods described, for example, inU.S. Pat. Nos. 2,777,872, 2,846,417, 3,411,912, 3,832,185, 4,012,437,Japanese Pat. Nos. 3832/70, 19951/70, 30293/71, 1040/74, and Polymer,Vol. 18, p. 1058 (1977), and so forth.

Synthesis examples of representative compounds which can be used in thepresent invention are illustrated below.

SYNTHESIS EXAMPLE 1 Synthesis of Compound (1)

94.5 g (1 mol) of monochloroacetic acid and 350 ml of methanol were putinto a reaction vessel and stirred while maintaining a temperature of 0°to 5° C. 193 g of a 28% methanol solution of sodium methylate wasgradually added dropwise thereto while maintaining a temperature of thesystem so as not to exceed 30° C. Then a solution mixture of 156.2 g (1mol) of 3-acylamidopropyl dimethyl amine and 300 ml of methanol wasadded thereto (0.5 g of phenothiazine was added as a polymerizationinhibitor). Then the mixture was heated so as to make the temperature ofthe system at 60° C. and stirred for 10 hours. The sodium chloride thusformed was removed by filtration, and the filtrate was crystallized in alarge amount of acetone. The identification of the compound was carriedout using NMR spectrum, elemental analysis, infrared absorptionspectrum, etc. The yield of the reaction was 145 g (68%).

SYNTHESIS EXAMPLE 2 Synthesis of Compound (2)

72.06 g (1 mol) of β-propiolactone and 250 ml of acetonitrile were putinto a reaction vessel and cooled the temperature of the system to -20°C. with stirring. A solution mixture of 170 g (1 mol) of3-methacrylamidopropyl dimethyl amine and 700 ml of acetonitrile wasadded dropwise thereto while controlling the temperature of the systemso as not to exceed -10° C. The reaction solution was allowed to standovernight at from 0° C. to 5° C. while white hydroscopic crystals weredeposited. The crystals were collected by filtration to obtain 202 g ofCompound (2) (yield: 84%). The structure of the compound was confirmedby NMR spectrum, elemental analysis, and infrared absorption spectrum.The melting point of the compound was 109° C. to 111° C.

SYNTHESIS EXAMPLE 3 Synthesis of Compound (20)

70 g (0.58 mol) of 1,3-propanesultone and 800 ml of ethyl acetate wereput into a reaction vessel and cooled to 10° C. with stirring. 50 g(0.46 mol) of 1-vinyl-2-methylimidazole was added dropwise thereto. Themixture was stirred for 1 hour at a temperature of 10° to 15° C. and thetemperature was gradually elevated and stirred at 50° C. for 5 days. Thecrystals thus deposited were collected by filtration and dried to obtain104 g of Compound (20) (yield 87%). The structure of the compound wasconfirmed by NMR spectrum, elemental analysis and infrared spectrum.

While the betaine compound according to the present invention can beadded to any layer of the photographic light-sensitive material, it ispreferably incorporated into a light-sensitive silver halide emulsionlayer or a layer adjacent thereto.

When the betaine compound is incorporated into a silver halide emulsionlayer, the betaine compound can be added at any stage of preparation ofthe emulsion, but it is preferred to add the compound during chemicalripening, or after chemical ripening but before coating of the emulsion.

The amount of the betaine compound used according to the presentinvention can be varied, depending upon the kind of silver halideemulsion, the kind of the compound used, etc., but it is preferably usedin an amount of from about 0.001 to 1 mol, and preferably from 0.01 to0.5 mol, per mol of silver halide.

The value of pAg (logarithm of the reciprocal of the silver ionconcentration) during chemical ripening of the silver halide emulsionused in the present invention is preferably from about 8.0 to 11.0.

During chemical ripening, other chemical sensitizers may be addedtogether with the compound of the present invention. Examples of suchchemical sensitizers are the gold compounds described, for example, inU.S. Pat. Nos. 2,399,083, 2,597,856, 2,597,915, etc.; reducing materialsas the amines, stannous salts, etc., described, for example, in U.S.Pat. Nos. 2,487,850, 2,518,698, etc.; the salts of noble metals asplatinum, palladium, iridium, rhodium, etc.; and sulfur compounds asthioureas, thiazoles, rhodamines, etc., described, for example, in U.S.Pat. Nos. 2,410,698, 2,278,947, 2,728,668, 3,656,955, 4,032,928 and4,067,740, West German Patent Application (OLS) No. 2,547,723, etc.

The silver halide used for the silver halide photographic emulsions ofthis invention includes silver bromide, silver iodobromide, silverchloroiodobromide, silver chlorobromide, and so forth.

The silver halide photographic emulsions of this invention may beprepared by the methods described in Chimie et Physique Photographique,edited by P. Glafkides (Paul Montel, 1967); G. F. Duffin, PhotographicEmulsion Chemistry (The Focal Press, 1966); and V. L. Zelikman, et al.,Making and Coating Photographic Emulsion (The Focal Press, 1964).

Also, a cadmium salt, a zinc salt, a lead salt, a thallium salt, aniridium salt or a complex salt thereof, a rhodium salt or a complex saltthereof, or an iron salt or a complex salt thereof may be present duringprecipitation or physical ripening of the silver halide grains in orderto improve contrast and reciprocity law failure property.

The silver halide photographic emulsions of this invention may containvarious compounds for preventing the formation of fog during theproduction of photographic materials, preserving or processing thephotographic materials, or for stabilizing the photographic propertiesof the photographic materials. For example, there are many compoundsknown as antifoggants or stabilizers, such as azoles as benzothiazoliumsalts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles,bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles,mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles,benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (in particular,1-phenyl-5-mercaptotetrazole), etc.; mercaptopyrimidines;mercaptotriazines; thioketo compounds as oxazolinethione; azaindenes astriazaindenes, tetraazaindenes (in particular, 4-hydroxy substituted(1,3,3a,7)tetraazaindene), pentaazaindenes, etc.; benzenethiosulfonicacid; benzenesulfinic acid; and benzenesulfonic acid amide. Among thesestabilizers, tetraazaindenes are particularly preferred. Thesestabilizers are preferably added during chemial ripening, or afterripening but before coating the silver halide emulsion.

The silver halide photographic emulsions of this invention may containan inorganic or organic hardening agent. For example, a chromium salt(chromium alum, chromium acetate, etc.), an aldehyde (formaldehyde,glyoxal, glutaraldehyde, etc.), an active vinyl compound(1,3,5-triacryloylhexahydro-S-triazine, etc.), an active halogencompound (2,4-dichloro-6-hydroxy-S-triazine, etc.), a mucohalogenicacid, etc., can be used.

Photographic couplers which can be used in the present invention includecompounds capable of forming dyes upon oxidative coupling with anaromatic primary amine developing agent (for example, a phenylenediaminederivative, an aminophenol derivative, etc.) in the color developmentprocessing. For instance, for magenta couplers, there are 5-pyrazolonecouplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers,open chain acylacetonitrile couplers, etc.; for yellow couplers, thereare acylacetoamide couplers (for example, benzoylacetanilides,pivaloylacetanilides, etc.), etc.; and for cyan couplers, there arenaphthol couplers, phenol couplers, etc.

The light-sensitive material of the present invention may containhydroquinone derivatives, aminophenol derivatives, gallic acidderivatives, ascorbic acid derivatives, etc., as color fog preventingagents.

The photographic emulsion layers and other hydrophilic colloid layers ofthe light-sensitive material according to the present invention maycontain a wide variety of known surface active agents for variouspurposes such as for improving coating property, preventing staticphenomenon, improving slipping property, improving emulsification anddispersion properties, preventing adhesion, as well as improvingphotographic characteristics (e.g., development acceleration,contrasting, sensitization, etc.).

Examples of these surface active agents are nonionic surface activeagents such as saponin (steroid series), alkylene oxide derivatives(e.g., polyethylene glycol, polyethylene glycol/polypropylene glycolcondensate, polyethylene glycol alkyl ether, polyethylene glycolalkylaryl ether, polyethylene glycol esters, polyethylene glycolsorbitan esters, polyalkylene glycol alkylamines, polyalkylene glycolalkylamides, polyethylene oxide addition products of silicones, etc.),glycidol derivatives (e.g., polyglyceride alkenylsuccinate, alkylphenolpolyglyceride, etc.), fatty acid esters of polyhydric alcohols, alkylesters of sugar, urethanes and ethers; anionic surface active agentscontaining acid groups as carboxy group, sulfo group, phospho group,sulfuric acid ester group, phosphoric acid ester group, etc., such astriterpenoidsaponin, alkylcarboxylates, alkylsulfonates,alkylbenzenesulfonates, alkylnaphthalene-sulfonates, alkylsulfuric acidesters, alkylphosphoric acid esters, N-acyl-N-alkyltaurines,sulfosuccinic acid esters, sulfoalkylpolyoxyethylene alkylphenyl ethers,polyoxyethylene alkylphosphoric acid esters, etc.; amphoteric surfaceactive agents such as amino acids, aminoalkylsulfonic acids,aminoalkylsulfuric acid esters, aminoalkylphosphoric acid esters,alkylbetaines, amine imides, amine oxides, etc.; and cationic surfaceactive agents such as alkylamines, aliphatic quaternary ammonium salts,aromatic quaternary ammonium salts, heterocyclic quaternary ammoniumsalts (e.g., pyridinium, imidazolium, etc.), phosphonium or sulfoniumsalts containing heterocyclic rings, and aliphatic phosphonium orsulfonium salts.

In the present invention, fluorine-containing surface active agents canalso be used. For example, fluorine-containing surface active agents asdescribed in British Pat. Nos. 1,330,356, 1,524,631, U.S. Pat. Nos.3,666,478, 3,589,906, Japanese Pat. No. 26687/77, Japanese PatentApplication (OPI) Nos. 46733/74, 32322/76 (The term "OPI" as used hereinrefers to a "published unexamined Japanese patent application"), etc.,can be used.

Typical examples of such fluorine-containing surface active agentsinclude N-perfluorooctylsulfonyl-N-propylglycin potassium salt,2-(N-perfluorooctylsulfonyl-N-ethylamino)ethyl phosphate,N-[4-(perfluorononenyloxy)-benzyl]-N,N-dimethylammonium acetate,N-[3-(N',N',N'-trimethylammonio)propyl]perfluorooctylsulfonamido iodide,N-(polyoxyethylenyl)-N-propylperfluorooctyl sulfonamide (C₈ F₁₇ SO₂ N(C₃H₇)(CH₂ CH₂ O)_(n) H) wherein n is from 1 to 50, and fluorine-containingsuccinic acid type compounds, and so forth.

Furthermore, the photographic light-sensitive materials using a silverhalide photographic emulsion according to the present invention cancontain a wide variety of additives for photography, such as antistaticagents other than the above-described surface active agents (forexample, ionic polymers as described, for example, in U.S. Pat. No.3,938,999, Research Disclosure, Vol. 162, page 48, etc.; metal oxides asdescribed, for example, in U.S. Pat. Nos. 3,062,700, 3,245,833 and3,525,621, etc., colloidal silica, etc.); polymer vehicles (for example,gelatin, gelatin derivatives, graft polymers between gelatin and otherpolymers, proteins such as albumin, casein, etc.; cellulose derivativessuch as hydroxyethyl cellulose, carboxymethyl cellulose, cellulosesulfates, etc.; sodium alginate, saccharide derivatives such as starchderivatives, etc.; and various synthetic hydrophilic polymericmaterials, for example, homo- or copolymers such as polyvinyl alcohol,polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polystyrenesulfonic acid, polyacrylic acid, polymethacrylic acid, polyacrylamide,polyvinylimidazole, polyvinylpyrazole, etc.); polymer latexes (forexample, polymers comprising, as the monomer component, individually orin combination, alkyl (meth)acrylates, alkoxyalkyl (meth)acrylates,glycidyl (meth)acrylates, (meth)acrylamides, vinyl esters (for example,vinyl acetate), acrylonitrile, olefins, styrene, etc., or combinationthereof with acrylic acid, methacrylic acid, α,β-unsaturateddicarboxylic acids, hydroxyalkyl (meth)acrylates, sulfoalkyl(meth)acrylates, styrene sulfonic acid, etc.), matting agents, whiteningagents, spectral sensitizing dyes, dyestuffs, etc. These additives, aswell as the supports for the photographic light-sensitive materials,coating methods, development processing methods for the photographicmaterials, etc., may refer to the descriptions of Research Disclosure,Vol. 92, pages 107 to 110 (1971, Dec.).

The silver halide photographic light-sensitive materials using aphotographic emulsion according to the present invention have highsensitivity as well as resulting in the formation of less fog. Also,when the photographic materials are preserved for a long period of timeunder high temperature and high humidity conditions, the reduction inphotographic properties such as the increase of fog with the passage oftime, the reduction in sensitivity, etc., is less.

The photographic light-sensitive materials to which the presentinvention can be applied are not restricted. For example, it can beapplied to ordinary black and white light-sensitive materials,light-sensitive materials for lithography, light-sensitive materials forX-ray, color negative light-sensitive materials, color papers, colorreversal light-sensitive materials, autopositive light-sensitivematerials, light-sensitive materials for diffusion transfer process, andso forth.

The present invention will be explained in greater detail with referenceto the following examples, but the present invention should not beconstrued as being limited thereto.

EXAMPLE 1

To a silver iodobromide gelatino emulsion (mean grain size of silverhalide grains being 1.3 microns) containing 1.5 mol% silver iodide, 0.6mg per mol of silver halide of chloroauric acid and 3.4 mg per mol ofsilver halide of sodium thiosulfate were added. The emulsion was heatedfor 50 minutes at 60° C. to perform ripening. To the silver halideemulsion thus obtained, 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene as astabilizer, 5-nitrobenzotriazole as an antifogging agent and further thecompound shown in Table 1 below were added and the resulting mixture wascoated on a film to prepare Samples 1 to 12, respectively. Each of thesesamples were exposed using a sensitometer and developed for 90 secondsusing a developer, RD-III (made by Fuji Photo Film Co., Ltd.) for anautomatic processer, Fuji-RN (made by Fuji Photo Film Co., Ltd.). Thephotographic properties of the samples were measured and the results areshown in Table 1 below. In Table 1, the sensitivity of Sample 1 wastaken as 100, and the other sensitivities are shown relatively.

                  TABLE 1                                                         ______________________________________                                                               Amount                                                                        Added      Sensi-                                      Sample No.                                                                             Compound      (g/mol AgX)                                                                              tivity                                                                              Fog                                   ______________________________________                                        1        --            --         100   0.03                                  (Blank)                                                                       (Present Compound (2)  8.5        129   0.04                                  invention)                                                                    3                                                                             (Present Compound (2)  17         135   0.03                                  invention)                                                                    4                                                                             (Present Compound (3)  8.5        115   0.04                                  invention)                                                                    5                                                                             (Present Compound (15) 8.5        117   0.02                                  invention)                                                                    6                                                                             (Present Compound (15) 17         122   0.01                                  invention)                                                                    7                                                                             (Present Compound (7)  8.5        110   0.03                                  invention)                                                                    8                                                                             (Present Compound (9)  8.5        115   0.04                                  invention)                                                                    9                                                                             (Present Compound (10) 8.5        115   0.04                                  invention)                                                                    10       Sodium p-Styrene                                                                            17         101   0.04                                  (Comparison)                                                                           Sulfonic Acid                                                        11       Acrylic Acid  17         90    0.03                                  (Comparison)                                                                  12       Dimethyl Dodecyl                                                     (Comparison)                                                                           Ammonio Acetate                                                                             8.5        100   0.04                                           Betaine*                                                             ______________________________________                                         ##STR5##                                                                 

It is apparent from the results shown in Table 1 above that Samples 2 to9 using the compounds according to the present invention has highsensitivity without an accompanying increase in the formation of fog. Onthe other hand, the compounds used for comparison did not show sucheffects.

EXAMPLE 2

An aqueous gelatin solution containing potassium iodide and potassiumbromide was maintained at 70° C. with stirring, and thereto an aqueoussolution of potassium bromide and an aqueous solution of silver nitratewere simultaneously added to prepare a silver iodobromide emulsio(containing 5 mol% silver iodide) having 0.8 micron mean grain size.

The silver halide emulsion was cooled, set, and washed with water toremov the unnecessary salts in a conventional manner. The pH value andpAg valu of the emulsion were adjusted to 6.5 and 8.9, respectively. Theemulsion was heated at 60° C., to which sodium thiosulfate and potassiumchloroaurate were added and subjected to chemical ripening for 60minutes

After adding the sensitizing dye, the stabilizer, the color coupler, thegelatin hardener, the coating aid described below, and the compounddescribed in Table 2 below, the silver halide emulsion was coated on acellulose acetate film support and dried.

Sensitizing Dye:5,5'-dichloro3,3'-di(γ-sulfopropyl)-9-ethyloxacarbocyanine sodium salt

Stabilizer: 4-hydroxy6-methyl-1,3,3a,7-tetraazaindene

Coupler:1-(2,4,6-trichlorophenyl)3-[3-(2,4-di-tertamylphenoxy)acetamido]benzamido5-pyrazolone

Gelatin Hardener: 2,4-dichloro6-hydroxy-s-triazine

Coating Aid: sodium dodecylbenzenesulfonate

Each of these samples was exposed (1/100 second) through an opticalwedge and subjected to the color development processing described below.The photographic properties of the samples were measured and the resultswere shown in Table 2 below.

In Table 2, the photographic sensitivity is shown by a reciprocal of theexposure amount required for obtaining an optical density of fog value+0.20 and the sensitivity of Sample 13 is taken as 100 and the othersensitivities are shown relatively.

    ______________________________________                                                       Temperature                                                    Processing Step                                                                              (°C.) Time                                              ______________________________________                                        1. Color development                                                                         38           3 min 15 sec                                      2. Bleach      "            6 min 30 sec                                      3. Wash        "            3 min 15 sec                                      4. Fix         "            6 min 30 sec                                      5. Wash        "            3 min 15 sec                                      6. Stabilization                                                                             "            3 min 15 sec                                      ______________________________________                                    

The compositions of the processing solutions used in the aboveprocessing were as follows:

    ______________________________________                                        Color Developer Solution:                                                     Sodium Nitrotriacetate  1.0      g                                            Sodium Sulfite          4.0      g                                            Sodium Carbonate        30.0     g                                            Potassium Bromide       1.4      g                                            Hydroxylamino Sulfate   2.4      g                                            4-(N-Ethyl-N-β-hydroxyethylamino)-                                                               4.5      g                                            2-methylaniline Sulfate                                                       Water to make           1        l                                            Bleaching Solution:                                                           Ammonium Bromide        160.0    g                                            Aqueous Ammonia (28%)   25.0     ml                                           Ethylenediaminetetraacetic Acid                                                                       130      g                                            Sodium Iron Salt                                                              Glacial Acetic Acid     14       ml                                           Water to make           1        l                                            Fixing Solution:                                                              Sodium Tetrapolyphosphate                                                                             2.0      g                                            Sodium Sulfite          4.0      g                                            Ammonium Thiosulfate (70%)                                                                            175.0    ml                                           Sodium Hydrogensulfite  4.6      g                                            Water to make           1        l                                            Stabilization Solution:                                                       Formalin                8.0      ml                                           Water to make           1        l                                            ______________________________________                                    

                  TABLE 2                                                         ______________________________________                                                              Amount                                                                        Added      Sensi-                                       Sample No.                                                                             Compound     (g/mol AgX)                                                                              tivity Fog                                   ______________________________________                                        13       --           --         100    0.10                                  (Blank)                                                                       14                                                                            (Present Compound (2) 8.5        120    0.10                                  invention)                                                                    15                                                                            (Present Compound (2) 17.0       140    0.11                                  invention)                                                                    16                                                                            (Present Compound (15)                                                                              8.5        125    0.10                                  invention)                                                                    17                                                                            (Present Compound (15)                                                                              17.0       130    0.11                                  invention)                                                                    18                                                                            (Comparison)                                                                           Acrylic Acid 17.0       95     0.10                                  19       Sodium p-Styrene                                                                           17.0       100    0.10                                  (Comparison)                                                                           Sulfonic Acid                                                        ______________________________________                                    

It is apparent from the results shown in Table 2 above that in Samples(14) to (17) according to the present invention the sensitivity isincreased without an accompanying increase in the formation of fog.

EXAMPLE 3

A silver halide emulsion containing 80 mol% silver chloride, 19.5 mol%silver bromide and 0.5 mol% silver iodide was subjected to goldsensitization and sulfur sensitization. The mean grain size of thesilver halide grains was 0.35 micron.

Then, 625 g each of the silver halide emulsion was placed in each of 10pots and after adding thereto the compound as shown in Table 3 below andfurther an appropriate amount of3-carboxymethyl-5-[2-(3-ethylthiazolinylidene)ethylidene]rhodanine(optical sensitizer), 4-hydroxy-1,3,3a,7-tetraazaindene (stabilizer), apolyoxyethylene compound described below (dot quality improving agent),mucochloric acid (hardening agent) and the polymer latex described inProduction Formulation 3 of Japanese Pat. No. 5331/70, and resultantmixture was coated on a polyethylene terephthalate film base to provideeach photographic light-sensitive material.

Each of these light-sensitive materials was brought into close contactwith a positive gray contact screen and exposed to a white tungstenlight for 10 seconds through a step wedge having a step differential of0.1. After exposure, the samples were developed for 100 seconds at 27°C. using the developer solution having the composition shown below, andfixed and washed with water in a conventional manner.

After processing, the dot quality was evaluated in four grades of A:excellent, B: acceptable in practical use, C: poor, and D: very poor, byobserving dots in 50% blackened areas with a microscope of 100magnifications.

Also, the sensitivity was evaluated by exposing, processing andsensitometry in the same manner as described above but without using acontact screen. The sensitivity was compared as the reciprocal of theexposure amount for obtaining the optical density of 1.50 and shownrelatively by defining the sensitivity of Sample 21 to be 100.

    ______________________________________                                        Developer Solution:                                                           ______________________________________                                        Hydroquinone              15 g                                                Addition Product of Formaldehyde                                                                        50 g                                                and Sodium Bisulfite                                                          Potassium Carbonate       30 g                                                Sodium Sulfite            2.5 g                                               Potassium Bromide         2.0 g                                               Boric Acid                5.0 g                                               Sodium Hydroxide          3.0 g                                               Triethylene Glycol        40 g                                                Ethylenediaminetetraacetic Acid . 2-                                                                    1.0 g                                               Sodium Salt                                                                   Diethanolamine            15 g                                                Water to make             1,000 ml                                            Polyoxyethylene Compound                                                       ##STR6##                                                                     ______________________________________                                    

                  TABLE 3                                                         ______________________________________                                                              Amount                                                                        Added            Dot                                    Sample No.                                                                             Compound     (g)      Sensitivity                                                                           Quality                                ______________________________________                                        21       --           --       100     C                                      (Blank)                                                                       22                                                                            (Present Compound (2) 6.0      115     B                                      invention)                                                                    23                                                                            (Present Compound (2) 12.0     124     A                                      invention)                                                                    24                                                                            (Present Compound (2) 24.0     125     A                                      invention)                                                                    25                                                                            (Present Compound (3) 6.0      117     B                                      invention)                                                                    26                                                                            (Present Compound (3) 12.0     125     A                                      invention)                                                                    27                                                                            (Present Compound (3) 24.0     125     A                                      invention)                                                                    28       Sodium p-Styrene                                                     (Comparison)                                                                           Sulfonic Acid                                                                              6.0      100     C                                      29       Sodium p-Styrene                                                     (Comparison)                                                                           Sulfonic Acid                                                                              12.0     100     C                                      30       Sodium p-Styrene                                                     (Comparison)                                                                           Sulfonic Acid                                                                              24.0     100     C                                      ______________________________________                                    

It is apparent from the results shown in Table 3 above that Samples (22)to (27) according to the present invention provide a high sensitivityand an excellent dot quality.

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A silver halide photographic light-sensitivematerial comprising a support having coated therein at least one silverhalide emulsion layer, said photographic light-sensitive materialcontaining a sensitizing amount of a compound represented by formula (I)##STR7## wherein R₁, R₂, and R₃ each represents hydrogen, an alkylgroup, a carboxy group, or a substituted alkyl group; R₄ and R₅ eachrepresents hydrogen, an alkyl group, a substituted alkyl group, or anaralkyl group, or R₄ and R₅ together represent an atomic group forming aheterocyclic ring or an atomic group forming a heterocyclic ringtogether with A; R₆, R₇, R₈, and R₉ each represents hydrogen, an alkylgroup or a substituted alkyl group; A represents a divalent connectinggroup which is an ether group, an alkylene group, a substituted alkylenegroup, an arylene group, a substituted arylene group, an aralkylenegroup, a substituted aralkylene group, a --COOR₁₀ -group, a --OCO--R₁₀-group, ##STR8## or an atomic group forming a heterocyclic ring togetherwith R₄ and R₅ ;wherein R₁₀ represents a divalent group selected from analkylene group, an arylene group, and an aralkylene group, or an atomicgroup forming a heterocyclic ring together with R₄ or R₅ ; and whereinR₁₁ represents hydrogen, an alkyl group, or an atomic group forming aheterocyclic ring together with R₄ and R₁₀, or R₅ and R₁₀ ; a and b caneach represents 0 or a positive integer, provided that a and b are notboth 0; and B represents --COO or --SO₃.
 2. A silver halide photographiclight-sensitive material as in claim 1, wherein said alkyl groupsrepresented by R₁ through R₉ each contains from 1 to 6 carbon atoms. 3.A silver halide photographic light-sensitive material as in claim 1,wherein said substituted alkyl groups represented by R₁ through R₉ eachis an alkyl group containing from 1 to 6 carbon atoms, and issubstituted with a member selected from a hydroxy group, a halogen atom,and a nitro group.
 4. A silver halide photographic light-sensitivematerial as in claim 1, wherein said aralkyl group represented by R₄ orR₅ has from 7 to 11 carbon atoms.
 5. A silver halide photographiclight-sensitive material as in claim 1, wherein said heterocyclic ringformed from R₄ and R₅ is a morpholine ring.
 6. A silver halidephotographic light-sensitive material as in claim 1, wherein saidheterocyclic ring formed from R₄, R₅, and A is a pyridine ring or animidazole ring.
 7. A silver halide photographic light-sensitive materialas in claim 1, wherein R₁, R₂, and R₃ each represents hydrogen, a loweralkyl group, or a carboxy group; R₄ and R₅ each represents a lower alkylgroup or an atomic group forming a pyridine ring or an imidazole ring,or R₄ and R₅ together represent an atomic group forming a morpholinering; R₆, R₇, R₈, and R₉ each represents hydrogen or a methyl group; Arepresents ##STR9## a --COOR₁₀ -group, or an atomic group forming apyridine ring or an imidazole ring together with R₄ and R₅ ; a and beach represents 0 or a positive integer from 1 to 4, provided that a andb are not both 0; and B represents --COO or --SO₃ ;wherein R₁₀represents a divalent group selected from an alkylene group, an arylenegroup, and an aralkylene group, or an atomic group forming aheterocyclic ring together with R₄ or R₅ ; and wherein R₁₁ representshydrogen, an alkyl group, or an atomic group forming a heterocyclic ringtogether with R₄ and R₁₀, or R₅ and R₁₀.
 8. A silver halide photographiclight-sensitive material as in claim 7, wherein R₁, R₂, and R₃ eachrepresents hydrogen, a methyl group, an ethyl group, or a carboxy group;R₄ and R₅ each represents a methyl group, an ethyl group, or an atomicgroup forming a pyridine ring, an imidazole ring, or R₄ and R₅ togetherrepresent an atomic group forming a morpholine ring; R₆, R₇, R₈, and R₉each represents hydrogen or a methyl group; A represents ##STR10## a--COO--R₁₀ -group, or an atomic group forming a pyridine ring or animidazole ring together with R₄ and R₅ ; a and b each represents 0 or apositive integer from 1 to 4, provided that a and b are not both 0; andB represents --COO or --SO₃ ;wherein R₁₀ represents a divalent groupselected from an alkylene group, an arylene group, and an aralkylenegroup, or an atomic group forming a heterocyclic ring together with R₄or R₅ ; and wherein R₁₁ represents hydrogen, an alkyl group, or anatomic group forming a heterocyclic ring together with R₄ and R₁₀, or R₅and R₁₀.
 9. A silver halide photographic light-sensitive material as inclaim 7, wherein R₁, R₂, and R₃ each represents hydrogen or a methylgroup; R₄ and R₅ each represents a methyl group or an ethyl group; R₆,R₇, R₈, and R₉ each represents hydrogen or a methyl group; A represents##STR11## or a --COOR₁₀ -group; a and b each represents 0, 1, or 2,provided that a and b are not both 0; and B represents --COO or --SO₃;wherein R₁₀ represents a divalent group selected from an alkylenegroup, an arylene group, and an aralkylene group, or an atomic groupforming a heterocyclic ring together with R₄ or R₅ ; and wherein R₁₁represents hydrogen, an alkyl group, or an atomic group forming aheterocyclic ring together with R₄ and R₁₀, or R₅ and R₁₀.
 10. A silverhalide photographic light-sensitive material as in claim 9, wherein R₁₀represents an alkylene group or an aralkylene group and R₁₁ representshydrogen or a methyl group.
 11. A silver halide photographiclight-sensitive material as in claim 9, wherein A represents ##STR12##and R₁₁ represents an atomic group forming a piperazine ring togetherwith R₄ and R₁₀, or R₅ and R₁₀.
 12. A silver halide photographiclight-sensitive material as in claim 1, wherein said compound is presentin a silver halide emulsion layer or a layer adjacent thereto.
 13. Asilver halide photographic light-sensitive material as in claim 1,wherein said compound is present in a silver halide emulsion layer. 14.A silver halide photographic light-sensitive material as in claim 1, 2,3, 4, 5, 6, 7, 8, 9, 10, 11, 12, or 13, wherein the amount of saidcompound is from about 0.001 mol to 1 mol per mol of silver halide inthe silver halide emulsion layer.
 15. A silver halide photographiclight-sensitive material as in claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11,12, or 13, wherein the amount of said compound is from 0.01 mol to 0.5mol per mol of silver halide in the silver halide emulsion layer.
 16. Asilver halide photographic light-sensitive material as in claim 13prepared by adding said compound to the silver halide emulsion during orafter chemical ripening thereof, but before coating of said emulsion.17. A silver halide photographic light-sensitive material as in claim16, wherein the pAg of the silver halide emulsion during chemicalripening is from about 8.0 to 11.0.
 18. A silver halide photographiclight-sensitive material as in claim 1, wherein said silver halideemulsion is chemically sensitized.